Triple para-Functionalized Cations and Neutral Radicals of Enantiopure Diaza[4]helicenes

Modulation of absorbance and emission is key for the design of chiral chromophores. Accessing a series of compounds absorbing and emitting (circularly polarized) light over a wide spectral window and often toward near-infrared is of practical value in (chir)optical applications. Herein, by late-stage functionalization on derivatives bridging triaryl methyl and helicene domains, we have achieved the regioselective triple introduction of para electron-donating or electron-withdrawing substituents. Extended tuning of electronic (e.g., E_1/2^red -1.50 V → -0.68 V) and optical (e.g., emission covering from 550 to 850 nm) properties is achieved for the cations and neutral radicals; the latter compounds being easily prepared by mono electron reductions under electrochemical or chemical conditions. While luminescence quantum yields can be increased up to 70% in the cationic series, strong Cotton effects are obtained for certain radicals at low energies (λ_abs ∼ 700-900 nm) with g_abs values above 10^-3. The open-shell electronic nature of the radicals was further characterized by electron paramagnetic resonance revealing an important spin density delocalization that contributes to their persistence.